Removal method of manganese from waste water

ABSTRACT

A removal method of manganese in which manganese is removed by precipitating manganese selectively from sulfuric acid waste water containing aluminum, magnesium and manganese with inhibiting the precipitation of magnesium. 
     The removal method of manganese from waste water in which manganese is removed by precipitating manganese selectively from the sulfuric acid waste water containing aluminum, magnesium and manganese with inhibiting the precipitation of magnesium, characterized in that said waste water is subjected to the following steps (1) and (2). 
     (1) First, aluminum in said waste water is removed. 
     (2) Subsequently, neutralizing agent is added into the wastewater after removing aluminum, then pH of the waste water is adjusted at 8.0 to 9.0, and oxygen gas is blown.

FIELD OF THE INVENTION

The present invention relates to a removal method of manganese from waste water, in more detail, a method in which manganese only can be efficiently removed by precipitating manganese selectively from sulfuric acid waste water containing aluminum, magnesium and manganese, with inhibiting the precipitation of magnesium.

DESCRIPTION OF THE PRIOR ART

In a treatment step of industrial waste water or the like, a technology in which heavy metal is separated from waste water, particularly, fixed as precipitate, is significantly important technology for environmental conservation. Among them, in the acidic waste water containing manganese as heavy metal, usually, fixation of manganese is not easy, therefore generally, it has been employed a method that considerable amount of slurry of calcium hydroxide which is generally industrially used, is used as neutralizing agent, and pH is adjusted at 8.0 to 10.0 of alkaline range, to form the precipitate and eliminate it. However, although manganese can be removed by this method, for example, when this method was applied to sulfuric acid waste water containing magnesium and manganese, there was a problem that amount of neutralizing agent which greatly exceed chemical equivalent for fixing manganese is needed because magnesium sulfate unnecessary for fixing is completely precipitated due to solubility.

As this countermeasure, the method that manganese can be preferentially removed from acidic solution containing magnesium and manganese is disclosed (for example, refer to Patent Literature 1). This method is one that when manganese is removed as precipitate from manganese acidic solution including 1 to 3 g/L of Mn and 2 to 15 g/L of Mg obtained by acid leaching of nickel oxide ore, manganese is preferentially precipitated and removed by controlling with the addition of air, oxygen, ozone or peroxide, so that pH of solution is adjusted at 8.2 to 8.8, as well as oxidation-reduction potential (mV) becomes to 50 to 300 mv. In this method, manganese can be oxidized, and can be more preferentially neutralized than magnesium to be removed as the precipitate, therefore, it is said that consumption amount of neutralizing agent is less. This is based on that when pH is about 8.0 of neutralizing condition, magnesium only cannot be precipitated out so much due to the solubility of magnesium hydroxide.

However, when this method is applied to the acidic solution containing aluminum besides magnesium and manganese, it was found that most of magnesium is co-precipitated with manganese. Therefore, there was a problem of increasing of use amount of neutralizing agent, and increasing of time of treatment, caused by neutralization precipitation of magnesium, also there was a problem that separation and recovery of manganese alone cannot be performed to utilize the precipitated manganese advantageously.

From the above situation, the method of removing manganese in which manganese can be selectively precipitated by inhibiting the precipitation of magnesium in the treatment step of sulfuric acid waste water containing aluminum, magnesium and manganese is needed.

PRIOR ART LITERATURE Patent Literature

-   Patent Literature 1: JP-3225836(page 1);

SUMMARY OF THE INVENTION

It is an object of the present invention to provide an efficient method for removing manganese only in which manganese is selectively precipitated by inhibiting the precipitation of magnesium from sulfuric acid waste water containing aluminum, magnesium and manganese, considering from the above-mentioned conventional technical problem.

The present inventors have intensively researched a method in which manganese only can be removed from sulfuric acid waste water containing aluminum, magnesium and manganese to achieve the above object. As a result, when aluminum and magnesium co-exist in the waste water at the same time, in the conventional treatment of oxidation neutralization, aluminum formed a complex hydroxide like a hydrotalcite and co-precipitated magnesium, as a result, it was found that consumption amount of neutralizing agent was increased. As a countermeasure for this problem, it was found that, firstly, after the step of removing aluminum from the waste water was carried out, subsequently, neutralizing agent was added into the waste water after removing aluminum to adjust the pH at 8.0 to 9.0, and also oxidizing-neutralizing treatment comprising the step of blowing oxygen gas was carried out, then manganese was selectively precipitated by inhibiting the precipitation of magnesium, namely, manganese only was able to be efficiently removed. And the present invention was completed.

That is, according to the first aspect of the present invention, there is provided a removal method of manganese from waste water in which manganese is removed by precipitating manganese selectively from the sulfuric acid waste water containing aluminum, magnesium and manganese with inhibiting the precipitation of magnesium, characterized in that waste water is subjected to the following steps (1) and (2).

(1) First, aluminum in the waste water is removed.

(2) Subsequently, neutralizing agent is added into the wastewater after removing aluminum, then pH of the waste water is adjusted at 8.0 to 9.0, and oxygen gas is blown.

In addition, according to the second aspect of the present invention, in the first aspect, there is provided the removal method of manganese from the waste water, characterized in that neutralization method, in which pH is adjusted at 4.0 to 6.0 by adding calcium carbonate or calcium hydroxide as a neutralizing agent in the step (1), is used.

In addition, according to the third aspect of the present invention, in the first aspect, there is provided the removal method of manganese from the waste water, characterized in that, in the step (2), first, after pH reaches equilibrium by adding neutralizing agent, subsequently oxygen gas is blown.

In addition, according to the fourth aspect of the present invention, in the first aspect, there is provided the removal method of manganese from the waste water, characterized in that, in the step (2), high-pressure vessel is used when oxygen gas is blown.

Also, according to the fifth aspect of the present invention, in any one of first to fourth invention, There is provided the removal method of manganese from the waste water, characterized in that, in the hydrometallurgical process in which nickel and cobalt are recovered from nickel oxide ore by High Pressure Acid Leach comprising leaching step in which leach solution is obtained by leaching nickel oxide ore with sulfuric acid; and sulfide precipitation step in which sulfides of nickel and cobalt is separated and recovered by adding hydrogen sulfide gas into the mother liquid after neutralizing the leach solution, the waste water is discharged from said sulfide precipitation step.

The removal method of manganese from the waste water of the present invention has very large industrial value because manganese only can be efficiently removed, in which manganese is selectively precipitated by inhibiting the precipitation of magnesium from sulfuric acid waste water containing aluminum, magnesium and manganese. Further, in the above step (2), first, neutralizing agent is added and after the pH equilibrium is reached, subsequently, oxygen gas is blown, consequently, consumption amount of neutralizing agent can be decreased, in addition, oxidation can be promoted by increasing amount of oxygen dissolved in the solution, provided that the high-pressure vessel is used when oxygen gas is blown, thus, this method is advantageous.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing a relationship between removal amount of magnesium to removal amount of aluminum.

FIG. 2 is a graph showing a change of Mn concentration, Mg concentration, Al concentration and Fe concentration in the solution by retention time.

FIG. 3 is a graph showing a change of Mn concentration by holding time (reaction time) accompanying with the pressure load of air or pure oxygen gas.

FIG. 4 is a graph showing a change of Mg concentration by holding time (reaction time) accompanying with the pressure load of air or pure oxygen gas.

FIG. 5 is a graph showing a change of Mn concentration, Mg concentration, Al concentration and Fe concentration in the solution by holding time.

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, the removal method of manganese from waste water of the present invention is described in detail.

The method for removing manganese from the waste water of the present invention is the removal method of manganese from waste water in which manganese is removed by precipitating manganese selectively from the sulfuric acid waste water containing aluminum, magnesium and manganese with inhibiting the precipitation of magnesium, characterized in that waste water is subjected to the following steps (1) and (2).

(1) First, aluminum in the waste water is removed.

(2) Subsequently, neutralizing agent is added into the wastewater after removing aluminum, then pH of the waste water is adjusted at 8.0 to 9.0, and oxygen gas is blown.

In the present invention, it is important to be subjected to the step of removing aluminum in the waste water (step (1)) is prior to the step of removing manganese in the waste water by neutralization (step (2)).

By this, in the above step, influence of aluminum can be excluded, therefore, manganese can be selectively precipitated by inhibiting the precipitation of magnesium. It should be noted that, in the step (1), aluminum concentration in the waste water after removal of aluminum is not particularly limited, and can be determined considering the acceptable amount of contamination of magnesium and aluminum into the manganese precipitate in step (2), for example, it is preferably 0.1 g/L or less, more preferably, 0.01 g/L or less.

That is, as a conventional technique, when oxidation neutralization treatment is carried out with keeping pH in 8.2 to 8.8 and adding oxidizing agent, aluminum in the solution is precipitated by forming complex hydroxide like hydrotalcite, not forming hydroxide. Here, the complex hydroxide co-precipitate magnesium, and contains up to six times equivalent of magnesium to aluminum. Therefore, since the manganese precipitates with the complex hydroxide at the same time, even when oxidation treatment is strengthened excessively, it is impossible to remove manganese selectively with inhibiting the precipitation of magnesium. Therefore, in the waste water, when ratio of content of magnesium to manganese is high, the complex hydroxide containing considerable amount of magnesium is generated, consequently, consumption amount of neutralizing agent is increased.

Hereinafter, the above effect of aluminum on the precipitation of magnesium is specifically described.

Here, sulfuric acid solution containing 3.4 g/L of Mn concentration, 8.4 g/L of Mg concentration, and 0.5 to 2.0 g/L of Al concentration, is added into a reactor (volume: 0.2 L), while the solution temperature is maintained at 50° C., slurry of calcium hydroxide having 20% by mass of concentration is added into the solution to adjust the pH at 8.0, pure oxygen gas is blown, and is left to stand for 30 minutes.

Consequently, as apparently from the relationship of the removal amount of magnesium to the removal amount of aluminum, ratio of magnesium/aluminum (molar ratio) becomes very high to be 2, even under the condition of pH in which magnesium hydroxide only cannot be formed as precipitate, magnesium can be probably neutralized and precipitated by forming the complex hydroxide like hydrotalcite.

In the above removal method, the step (1) is not particularly limited, various separation method that aluminum can be separated and removed from the sulfuric acid waste water containing aluminum, magnesium and manganese, can be used, among them, it is easy to use the neutralization method in which cheap calcium carbonate or calcium hydroxide is added as neutralizing agent to adjust the pH at 4.0 to 6.0. Here, when pH is less than 4.0, generation of precipitate of aluminum is insufficient, alternatively, when pH becomes more than 6.0, aluminum is co-precipitated with magnesium caused by local increase of pH due to neutralization agent, then, amount of precipitate increases. In this pH range, precipitation form of aluminum is aluminum hydroxide, consumption amount of neutralizing agent can respond equal to the theoretical equivalent.

Here, concentration of aluminum in waste water after removal of aluminum can be obtained as 0.01 g/L or less.

In the above removal method, although the step (2) is the step to remove as precipitate by oxidizing manganese from divalent to trivalent, neutralizing agent is added to the waste water after removal of aluminum obtained in the step (1), to adjust the pH at 8.0 to 9.0, and oxygen gas is blown, thus, manganese is removed as precipitate. In this case, first, neutralizing agent is added, after the pH equilibrium is reached, subsequently, oxygen gas is preferably blown. That is, in the addition of solid neutralizing agent having slow reactivity, after reaching the pH equilibrium, oxygen gas is blown, thus, consumption amount of neutralizing agent can be reduced.

Here, as oxidizing agent, ones having stronger oxidizing ability than that of air such as oxygen gas, ozone, peroxides are used, and practically, oxygen gas is used, particularly, industrial oxygen gas having less concentration of the other gas (for example, purity of oxygen: about 98% or more) is preferable, blowing amount thereof is selected from the sufficient amount for oxidizing manganese in the solution from divalent to trivalent.

It should be noted that, although the above neutralizing agent is not particularly limited, industrially cheap slurry of calcium hydroxide is preferable.

Therefore, as equipment of the step (2), it is preferable to provide separately the exclusive vessel for neutralization and the exclusive vessel for oxidation. Here, retention time in the above vessel for neutralization is industrially preferably 30 minutes or more to reach the pH equilibrium, when slurry of calcium hydroxide is used. By using this equipment, magnesium cannot be fixed as hydroxide on high-pH parts of the solid surface of calcium hydroxide, therefore, consumption amount of the neutralization agent caused by magnesium can be controlled. In addition, amount of manganese which co-precipitates in the neutralization divalent hydroxide without being oxidized can be reduced, thus, equilibrium concentration of manganese can be reduced, with more certainty, removal of manganese can be carried out.

In the above step (2), when oxygen gas is blown, for example, high-pressure vessel can be preferably used as the above vessel for oxidation. That is, since oxygen gas is generally difficult to be dissolved in the solution having high salt concentration like the waste water, it is useful for accelerating oxidation that amount of dissolved oxygen in the solution is increased by increasing the partial pressure of oxygen with using high-pressure vessel. Here, when partial pressure of oxygen is low, oxidation rate of manganese is effected by this pressure, thus, oxidation is preferably carried out under the suitable partial pressure of oxygen for obtaining the desired oxidation rate.

The sulfuric acid waste water containing aluminum, magnesium, and manganese to be used in the above removal method is not particularly limited, but the waste water is preferably used in which aluminum concentration is a concentration which induces to co-precipitate with magnesium at the undesired level when manganese is generated as precipitate by the above treatment of oxidation neutralization. For example, it is particularly useful that magnesium is contained at the same or higher concentration compared with that of manganese, and aluminum is contained at 1/100 or higher concentration of manganese.

Such an waste water is not particularly limited, but for example, in the hydrometallurgical process of recovering nickel and cobalt from nickel oxide ore, by High Pressure Acid Leach comprising leaching step of nickel oxide ore by sulfuric acid, sulfide precipitation step of nickel and cobalt from leach solution, the waste water discharged from said sulfide precipitation step is preferably exemplified.

As the hydrometallurgical method, in more detail, for example, the method comprising leaching step in which leach solution containing impurity element in addition to nickel and cobalt can be obtained by leaching nickel oxide ore with sulfuric acid under the elevated pressure at high temperature; neutralization step in which calcium carbonate is added to said leach solution to form a neutralization precipitate slurry including Fe (III) and a mother liquid for recovering of nickel; sulfide precipitation step in which hydrogen sulfide gas is added to said mother liquid for recovering of nickel to generate sulfides of nickel and cobalt, and separate and recover; and the treatment step of waste water after separating said sulfides, has been used. Here, the resultant waste water is, for example, sulfuric acid solution containing 2 to 6 g/L of Mn concentration, 3 to 12 g/L of Mg concentration, and 2 to 6 g/L of Al concentration, and is preferably used for removal method of the present invention.

EXAMPLES

Hereinafter, the present invention is described in more detail by using examples and comparative examples of the present invention, however, the present invention is not particularly limited by these examples. It should be noted that, metal analysis used in examples and comparative examples are carried out by ICP emission spectrometry.

Example 1

First, removal of aluminum (step (1)) was carried out. Waste water having 2.90 g/L of Mn concentration, 7.81 g/L of Mg concentration, 2.90 g/L of Al concentration, and 0.40 g/L of Fe concentration, which was obtained from sulfide precipitation step in hydrometallurgical process by the above High Pressure Acid Leach, was added to the reactor (volume: 2 L), and slurry of calcium hydroxide having 20% by mass of concentration was added to adjust the pH at 4.5, and after neutralization treatment, aluminum was removed. Here, aluminum concentration in the waste water after removing aluminum was 0.01 g/L.

Subsequently, removal of manganese (step (2)) was carried out. Waste water after removing aluminum was added to the reactor (volume: 2 L), while the solution temperature maintained at 50° C., slurry of calcium hydroxide having 20% by mass concentration was added to adjust the pH at 8.0, oxygen gas was blown at the rate of 1,000 mL/minute and retention time was changed, and, Mn concentration, Mg concentration, Al concentration and Fe concentration in the solution were measured. Results are shown in FIG. 2. FIG. 2 shows change of Mn concentration, Mg concentration, Al concentration and Fe concentration in the solution by retention time.

From FIG. 2, it was found that in the wastewater after removing aluminum, manganese was reduced to low concentration level over time, on the other hand, concentration change of magnesium was small. That is, manganese was selectively removed to magnesium. It should be noted that, although concentration of magnesium was decreased at the beginning of reaction, this was caused by the solubility of magnesium hydroxide, and parts having more than upper limit of this concentration showed to be precipitated immediately.

Example 2, Comparative Example 1

In removal of manganese (step (2)), except that slurry of calcium hydroxide was added in one portion before oxidation reaction to adjust the pH at 8.6, and oxygen gas was blown by using air (comparative example 1) or oxygen gas under the pressure load of 0.02 to 0.2 MPa (Example 2), the same manner as Example 1 was carried out, then, Mn concentration and Mg concentration in the solution was measured. Results are shown in FIGS. 3 and 4. FIG. 3 shows the change of Mn concentration by retention time (reaction time) accompanied with pressure load of air or oxygen gas. In addition, FIG. 4 shows the change of Mg concentration by retention time (reaction time) accompanied with pressure load of air or oxygen gas.

It is found that by FIG. 3, oxidation precipitation of manganese is accelerated by pressure load of oxygen gas, and reduction lower limit can be surely decreased. On the other hand, it is found that incase of air (comparative example 1), reaction rate is slower than that of oxygen gas.

From FIG. 4, it is found that magnesium is not reduced at equal of or under the certain amount of solubility determined by pH. That is, in precipitation of manganese, excellent selectivity for magnesium is obtained.

Comparative Example 2

Except that removal of aluminum (step (1)) was not carried out, the same manner as example 1 was carried out, and, Mn concentration, Mg concentration, Al concentration and Fe concentration in the solution were measured. Results are shown in FIG. 5. FIG. 5 shows the change of Mn concentration, Mg concentration, Al concentration and Fe concentration in the solution by retention time.

From FIG. 5, it is found that when aluminum co-exists in the waste water, magnesium is more preferentially precipitated than manganese.

From the above, in example 1 or 2, when manganese is removed from sulfuric acid waste water containing aluminum, magnesium and manganese, first, aluminum in the waste water is removed, subsequently, neutralization agent is added to the waste water after removing aluminum to adjust the pH at 8.0 to 9.0, then, oxygen gas is blown. Thus, since this was carried out according to the method of the present invention, it is found that manganese can be selectively precipitated by inhibiting the precipitation of magnesium, and manganese can be efficiently removed. On the other hand, in comparative example 1 or 2, it was found that, air was used instead of oxygen gas, or aluminum removing step was not carried out, and they did not match with these conditions, therefore, satisfied results were not obtained by the precipitation formation of manganese or the precipitation of magnesium.

As apparently from the above, the removal method of manganese from the waste water of the present invention can be used for the removal step of heavy metal of the waste water containing aluminum and magnesium, because manganese can be selectively removed to magnesium when manganese is removed from sulfuric acid waste water containing aluminum, magnesium and manganese. 

1. A removal method of manganese from waste water in which manganese is removed by precipitating manganese selectively from the sulfuric acid waste water containing aluminum, magnesium and manganese with inhibiting the precipitation of magnesium, characterized in that said waste water is subjected to the following steps (1) and (2). (1) First, aluminum in said waste water is removed. (2) Subsequently, neutralizing agent is added into the wastewater after removing aluminum, then pH of the waste water is adjusted at 8.0 to 9.0, and oxygen gas is blown.
 2. The removal method of manganese from the waste water according to claim 1, characterized in that neutralization method, in which pH is adjusted at 4.0 to 6.0 by adding calcium carbonate or calcium hydroxide as a neutralizing agent in said step (1), is used.
 3. The removal method of manganese from the waste water according to claim 1, characterized in that, in said step (2), first, after pH reaches equilibrium by adding neutralizing agent, subsequently oxygen gas is blown.
 4. The removal method of manganese from the waste water according to claim 1, characterized in that, in said step (2), high-pressure vessel is used when oxygen gas is blown.
 5. The removal method of manganese from the waste water according to any one of claims 1 to 4, characterized in that, in the hydrometallurgical process in which nickel and cobalt are recovered from nickel oxide ore by High Pressure Acid Leach comprising leaching step in which leach solution is obtained by leaching nickel oxide ore with sulfuric acid; and sulfide precipitation step in which sulfides of nickel and cobalt is separated and recovered by adding hydrogen sulfide gas into the mother liquid after neutralizing the leach solution, the said waste water is discharged from said sulfide precipitation step. 